Triazine derivatives

ABSTRACT

New 1,3,5-triazinyl-(6)-phosphonates are used as antioxydants for organic materials. They are prepared by reacting a corresponding 1,3,5-triazinyl-(6)-halogenide with a corresponding phosphonate.

iJited States Luet-hi et al.

atent H 1 [451 Aug. 19, 1975 TRIAZINE DERIVATIVES Inventors: ChristianLuethi, Muenchenstein;

Hans Rudolf Biland, Gelterkinden', Max Duennenberger, Frenkendorf, allof Switzerland [73} Assignee: Ciba-Geigy Corporation, Ardsley,

22 Filed: Nov. 14,1973

21 Appl. No.: 415,715

Related US. Application Data [62] Division of Ser. No. 156,541, June 24,1971,

"abandoned.

[30] Foreign Application Priority Data June 30, 1970 Switzerland 9877/70[52] US. Cl. 260/45.8 NT; 260/248 CS Primary ExaminerMelvyn l. MarquisAttorney, Agent, or FirmNester W. Shust [5 7 ABSTRACT Newl,3,5-triazinyl-(6)-phosphonates are used as antioxydants for organicmaterials. They are prepared by reacting a corresponding 1 ,3,5-triazinyl-( 6 halogenide with a corresponding phosphonate.

'10 Claims, N0 Drawings 1. TRIAZINE DERIVATIVES This application is adivision of application Ser. No.

156,541, filed June 24, 1971, now abandoned.

I DETAILED DESCRIPTION wherein A and A are identical or different, andeach represent an optionally substituted phenylene radical which isbound in position I to Z or toZ' and'carries in position 4 a hydroxylgroup; Z and Z are identical or different and represent a bridgingmember O, -S or ,-NQ-, with Q standing for hydrogen, alkyl, alkoxy, orCN; R and R are identical or different and each represent an optionallysubstituted alkyl, cycloalkyl or phenyl radical;

Suitable substituents on the phenylene radicals are, in the first place,alkyl or cycloalkyl, whereby by the term alkylis meant both branched andunbranched aly I Of predominant interest are triazine derivatives of theformula:

wherein R and R are identical or different and represent an alkyl grouphaving I to 8 carbon atoms; R and wherein R represents an alkyl grouphaving I to 4 carbon atoms, and R represents hydrogen or an alkyl grouphaving 1 to 4 carbon atoms, and R and X have the given meaning; thecompounds of the formula:

wherein R R R and X have the given meaning; the compounds of theformula:

wherein X and R have the given rneaning. In these formulae R preferablyrepresents astraight-chain alkyl grouphaving l to 18, especially 1 to 4,carbon atoms.

The compounds of formula (1) are advantageously produced by thereaction'of a compound of the formula:

wherein Hal represents a halogen atom, and A, A, Z and Z have the givenmeaning, with a compound of the formula:

wherein R and R have the given meaning, and R" is equal to or differentfrom R and R, and represents an optionally substituted alkyl,cycloalkyl, or phenyl radical.

The triazine derivatives of formula (2) are produced by the reaction ofa compound of the formula:

wherein Hal represents a halogen atom, and R R,, R R X and X have thegiven meaning, with a phosphite of the formula wherein R has the givenmeaning.

In the formulae (7) and (9), halogen is preferably chlorine.

The reaction can be performed in a solvent or solvent mixture inert tothe reactants. Suitable solvents are, e.g.: dichlorobenzene,trichlorobenzene, perchloroethylene, diethylene glycol dialkyl ether,p-cymol Preferably, however, the reaction is performed in the melt,whereby it is advantageous for the operation to be carried out in aninert atmosphere, e.g. under nitrogen. The reaction is thereby performedbetween 40 and 220C, preferably between 100 and 200C, whereby thereaction duration can be from several minutes to several hours,generally it is from half an hour to hours. The duration of the reactiondepends mainly on the chosen reaction temperature. On the other hand,the reaction duration depends also on the extent to which the halideformed during the reaction, generally a chloride, is removed from thereaction mixture to effect the displacement of the equilibrium in favourof the triazine derivatives according to the invention. For the purposeof removal of the halide by means of distillation, the reaction is henceadvantageously performed (particularly if higher-molecular halides areformed) under reduced pressure. Any solvent present therebysimultaneously distills off, so that the compounds according to theinvention remain behind, after completion of the reaction, direct in amore or less pure state.

The monohalogen triazines to be used as starting materials for thepresent process are accessible in a manner known per se, e.g., asdescribed in the US. Pat. No. 3,255,191.

The described new compounds constitute valuable antioxidants, i.e., theyare suitable for the stabilisation of organic materials to oxidativedecomposition, by which is meant, in particular, thermally acceleratedoxidations. Examples of materials which can be protected are:

1. Polymers derived from singly or doubly saturated hydrocarbons, suchas polyethylene which can be optionally cross-linked, polypropylene,polyisobutylene, polyme'thylenebutene- 1 polymethylpentenel polybutene-lpolyisoprene, polybutadiene, polystyrene, polyisobutylene;

copolymers of the monomers on which the mentioned homopolymers arebased, such as ethylene-propylene-copolymers, propylenebutenel-copolymers, propylene-isobutylene-copolymers,styrene-butadienecopolymers, as well as terpolymers of ethylene andpropylene with a diene, such as, .e.g., hexadiene, dicyclopentadiene orethylidenenorbonenes; mixtures of the above stated homopolymers such as,e.g., mixtures of polypropylene and polyethylene, polypropylene andpoly-butene-l, polypropylene and polyisobutylene.

2. Halogen-containing vinylpolymers such as polyvinyl chloride,polyvinylidene chloride, polyvinyl fluoride, also polychloroprene andchlorinated rubbers.

3. Polymers derived from a,/3-unsaturated acids and their derivatives,such as polyacrylates and polymethacrylates, polyacrylamides andpolyacrylonitrile, as well as their copolymers with other vinylcompounds, such as acrylonitrile/butadiene/styrene,acrylonitrile/styrene and acrylonitrile/styrene/acrylic estercopolymerisates.

4. Polymers derived from unsaturated alcohols and amines on their arylderivatives or acetals, such as polyvinyl alcohol, polyvinylacetate,-stearate, -benzoate, -maleate, polyvinylbutyral, polyallylphthalate,polyallylmelamine and copolymers thereof with other vinyl compounds,such as ethylene/vinylacetate copolymers.

5. Homoand copolymers derived from epoxides, such as polyethylene oxideor the polymerisates derived from bisglycidyl ethers.

6. Polyacetals, such as polyoxymethylene and polyoxyethylene, as well assuch polyoxymethylenes which contain as comonomer ethylene oxide.

7. Polyphenylene oxides.

8. Polyurethanes and polyureas.

9. Polycarbonates.

l0. Polysulphones.

ll. Polyamides and copolyamides derived from di amines and dicarboxylicacids and/or from aminocarboxylic acids or from the correspondinglactams, such as polyamide 6, polyamide 6/6, polyamide 6/10, polyamidell, polyamide l2.

l2. Polyesters derived from dicarboxylic acids and from dialcohols,and/or from hydroxycarboxylic acids or from the corresponding lactones,such as polyethylene glycol terephthalate,poly-l,4-dimethylolcyclohexaneterephthalate.

l3. Cross-linked polymerisates derived from aldehydes on the one hand,and from phenols, ureas and melamines, on the other hand, such asphenol- 16. Natural polymers such as cellulose, rubber, proteins; aswell as their.polymer-modified derivatives, such as cellulose acetates,cellulose propionates and cellulose butyrates, or the cellulose ethers,such asmethyl cellulose.

To obtain a good antioxidant effect, an amount of 0.01 to preferably 0.1to 2%, relative to the substrate to be protected, of the compoundsaccording to the invention generally suffices. The antioxidants can andmixtures thereof with melamine-formaldehyde resln the description and inthe examples, the term parts denotes, if not otherwise stated, parts byweight,

and percentages are always per cent by weight. The

melting points of the new compounds are not corrected.

EXAMPLE 1 l 1.1 Parts of the compound of the formula:

are heated together with 8.3 parts of triethyl phosphite in a nitrogenatmosphere for 3 hours to 140 to 145C. The obtained melt is thereupondissolved in parts of chloroform; to the solution are then added partsof hexane, the whole is concentrated to half the volume, and cooled to0C. The thereby precipitated product is filtered off under suction, andwashed with hexane. Thus obtained are 1 L3 parts of the compound of theformula:

be incorporated into the materials to be protected ei- 45 Melting point143C.

ther as antioxidants on their own or as mixtures with other additivessuch as softeners, pigments, agents protecting against light rays(UV-absorbers), further antioxidants, optical brighteners, with orwithout the aid of solvents.

The good stabilising effect of the new compounds is shown, for example,under accelerated ageing conditions at temperatures of above l00C. Apolypropylene subjected to these conditions and containing anantioxidant exhibits only after a very much longer period of .55

time signs of a discolouration, or of becoming brittle, compared withthe time taken for these effects to become apparent in the caseof apolypropylene not containing a stabiliser.

The compound of formula (ll) used as starting product and having amelting point of 217 to 219C is obtained in 86% yield by reaction of18.5 parts of cyanuric chloride with 44.5 parts of2,6-di-tert.butylhydroquinone in 250 parts of acetone, this beingeffected by the adding dropwise at 35 to 40C, in the course of 5 hours,of a solution of 8 parts of sodium hydroxide in parts of water, theaddition being made in such a way that the p -value does not exceed 7.The obtained suspension is thereupon cooled to 0C, the precipitatedproduct filtered off under suction, washed with water and dried.

In an analogous manner are obtained with use of the compounds of theformulae:

the compounds of the formulae:

Melting point 108 (decomposition) CH. 7 M 5 5 N C(CH I O on 1: mon i, rfl C Cl! may 1 3 O P C Stahiiiser No.2 oc i-1 l-ielting point up to 212213"c EXAMPLE 2 heated under vacuum (0.5 Torr) to 180C, and the formedoctadecyl chloride distilled off. The reaction is completed after 30minutes. Thus obtained are l 1 parts 5.5 Parts of the compound offormula 1 l are 55 of a yellow viscous oil from which is isolated, aftermelted together with 9.1 parts of trioctadecylphosphite chromatographyon silica gel and extraction with chlo- Stabilfiser N0 .10

in a nitrogen atmosphere at 50C. The melt is then roform, the compoundof the formula:

CH, C 5

11o{ i-oe c-0 C ll CY ,C 3%

0C Ha l/ 18 97 O P Melting point after recl'ystallisationfromacetone/wa- Melting point 95 to 96C.

In an analogous manner can be obtained by use of the ter=40 to 41C.

In an analogous manner is obtained the compound of l kelt ig pg ip gz259" to 260C Calculated: (2 70. 10 11 1-1 :S I Y I Found} 70. 46 10.06.53

liglti yilw 17 Calculated: 8-33 H 9- 7 N Found: 68.06 9.31 5.2]

3) C(cn Stabiliser No .19

Melting point 207' 208C The following prior known stabilisers weretested as comparison compounds in the application examples:

2,6-di'tert.butyl-4-methylphcnol Stabiliser No.20 methylene-bis-(3-'methyl-4-hydroxy- -tert.butylbenzene) Stahiliser No.21 thio-bis'-(2-methyl-4-hydroxy- 5-tert.butylbenzene) StabiliserZ No.23

Stabiliser No.24

Stabiliser No.25

EXAMPLE 3 y A mixture of 100 parts of unstabilised polypropylene (Profax6501, Hercules Powder) and 0.2 parts of a compound according to Table Agiven below is processed on a calendering machine at 170C into a sheet,and this subsequently pressed at 230C, under a pressure of 40 kg/cm, toform a plate of l mm thickness. The thus obtained plates are subjectedat 140C (air, normal pressure) to an accelerated oxygen ageing. The timepassing before the occurrence of the first cracks perceptible to the eyeis a measure for the antioxidative effect of the added compound.

TABLE A Added compound Time in hours EXAM PLE 4 100 Parts ofpolypropylene (melt index 3.2) are kneadedin a Brabender plastograph forminutes at 200C together with the stabilisers listed in the followingTables B and C. A homogeneous dispersion of the stabilisers is thusensured. The niass obtained-inthis manner is subsequently pressed in aplaten press, ,at 260C platen temperature, to form 1 mm thick plates.From the thus obtained plates are cut, with the aid of a microtome,chips having a thickness of 25 p... These chips are clamped betweenpieces of stainless steel mesh, and these specimen holders are thensuspended in 'an air circ'ulation furnace and aged at 135C or 147C.Taken as the final point of the test is the-point of timeat which alight tapping of the stainless steel mesh causes decomposedpolypropylene to fall out in powder form (control 1-2 times daily).Results: see Tables B and C."

TABLE B Added compound occurs, in hours at 135 at 147 without addition20 10 A. Commercial antioxidants 5 B. Compounds according to v theinvention 0.2% l 165 65 0.2% I 3 165 65 0.2% 10 230 95 r 0.2% 1 l 310120 0.2% 17 380 160 10 TABLE C Added compound Time until decomposition(Stabiliser No.) occurs, in hours at 135 at 147 0.1% 20 +03% DLTDP* 4015 0.1% 21 +03% 60 20 0.1% 22 0.3% 140 48 20 25'dilaurylthiodipropionatc EXAMPLE 5 Stabilisation of low-pressurepolyethylene 3 38 g of low-pressure polyethylene are kneaded togetherwith 0.1% of one of the additives listed in Table D in a Brabenderplastograph, whereby the torsional moment produced by the resistance tokneading is continuouslyrecorded. The decomposition of the polymer isindicated by a rapid decrease of the torsional moment after an inductionperiod characteristic for the additive.

, TABLE D Stabilrser No. Induction period In mm.

without addition 20 1 50 2 40 IO 65 EXAMPLE 6 Stabilisation of polyamide6 100 Parts of polyamide 6 granulate are mixed with 0.5 parts oftris-nonylphenylphosphite and 0.5 parts of one of the additives listedin Table E; the mixture is processed in Laborgelimat, a mixing devicewherein the composition is melted due to rapid mixing withoutapplication of heat, and afterwards pressed at 260C to form 1 mm thicktest plates. The plates are subjected to an air-circulation furnace at140C to an accelerated ageing treatment. The stabilising effect of theadditives is assessed according to the brittleness of the samples.

TABLE E Stabiliser No. Brittle after:

(hours) 5 without addition 18 l 25 2 34 3 34 l l 27 EXAMPLE 7 An amountof 100 g of unstabilised Polyamide 12 granulate (Vestamid L 1901 fromthe firm Chem. Werke Huels) is thoroughly mixed with 1.0 g of one of thestabilisers listed in the following Table Fg'the mixture is processedina Labor-Ge1irnat,'and then pressed out in a platen press at 260C toform 1 mm thick test plates. The plates are tested with respect tostability to furnace ageing at 150C after 2,5, 10, and 20 days bydetermination of the. viscosity of 0.5% m-cresol solutions. Anunstabilised comparison specimen, otherwise processed in an identicalmanner, is tested along with the stabilised specimens. The relativeviscosity, values (viscosity of the solution divided by the viscosity ofthe EXAMPLE Stabilisation of polyurethane 0.25 Parts ofthe additivesgiven in.Table.,H are in each case dissolved in the cold state in 100parts of a 25% polyurethane solution (ESTANE 5707 from the firmGoodrich").

From these solutions are drawn on' a glass plate using a film-drawingapparatus ca. 400 u thick films, which dry out, after I 10 minutesair-circulation drying at l40C, to form films having a final thicknessof .100 11.. The stabilisers' are accordingly present in the films in aconcentration of 10%. Specimens of these films are exposed on a whitecardboardrbackground in a Xenotest pure solvent at the sanietemperature) after the given apparatusuntil the occurrence of a visuallyperceptible furnace ageing times are shown in Table F. ye1lowirig'.' l

Stabiliser No. Relative viscosity in m-cresol after furnace ageing atafter 0 days after 2 days after 5 days after days after days withoutaddition 1.81 1.60 1.48 1.43 K

, 9 i 1.83 1.87 1.85 1.62, 1.54 10 1.86 1.90 1.84 1.76 1.60 11 I 1.84 I1.89 1.82 1.70 156 {19: 1.84 1.86" 1.86 1.68 1.55

EXAMPLE 8 1 TABLE 11 f Stabilisation of s y 'n thetic'i'ubbehEPDM i 5Stabiliser No. Exposure time in hours until Commercial EPDMz. rubber of,the firm Dutch yellowing clearly occurs Staatsmjinen is separated fromthe stabiliser by diswith! addition 150 solving in hot toluene andprecipitation with methanol. 25 250400 v Specimens each weighing 40 g ofthe dried, stabiliser- 2 300 free material are kneaded together with0.2% of one of 40 2 Z 300 600 the additives listed in Table G in aBrabender plasto- 9 +25 5004300 graph, whereby the torsional momentproduced by the 11 300 11 25 500-600 resistance to kneading iscontinuously recorded (Table: 19 350 torsional moment read off direct onthe balance in 19+25 600 grams). One specimen is tested at the same timewith respect to the gel content in. each case after 7.15 and EXAMPLE 1025 minutes (insoluble constituents in hexane). The gel contents increasewith progressive ageing, i.e., crosslinking of the polymer.

I y TABLE G S tabiliser'No. Torsional moment in grams after?- 7 min. 5min. 25 min.

, without addition l 3900 3300 2600' 10 i 3800 3450 3400" Gel content inpercent after:

Elastomer fibr'es of a linear polyurethane (Enkaswing SSAof FafAKU,Hollan'df'ar spun from a 20% dimethylac'etamide solution,a'nd the fibresprecipitated in a toluene bath. To the precipitation-bath are added:

1.5% of-Stabiliser No.- 10, Y

115' of 2-(2'-hydroxy-3,5'-di-tert.butylphenyl)-5-*ichlorobenzotriazole; 1 -.5 of dilaurylthiodipropionate; v 2.0% ofethylenediamine,

i 2.0%of silicone oil.

Used as'comparison specimen is a fibre produced in a similar manner butwithout addition of the antioici-- 6 0 dant according to theinventio'nto the'pr'e'cipitation bath. -Both fibre specimens are artificially agedfor 15 hours at C in a drying cupboard, whereby. it is observed that theunstabilised fibre clearly yellows, whereas the stabilised fibreexhibits no sign of yellowing,

EXAMPLE 1 l Stabilisation of polyacetal 100 Parts of an unstabilisedhomo-polyacetal (polyformaldchyde, origin: Societa Italiana Resine) aremixed with 1.5 parts of calcium stearate and 0.2 parts of one of theadditives listed in Table 1; the mixture is then processed for 15minutes on a two-roller mill, and the rolled sheet drawn off. An amountin each case of 10 mg of the stabilised specimens is heated on the panof a sensitive thermo-balance to 220C. The loss in weight (in per cent)of the specimens is continuously recorded.

TABLE] Stabiliser No. Loss in weight in after:

5 min. 10 min. 15 min.

without addition 12 22 31 l 3 9 l3 l l2 17 ll 4 10 17 7 l2 1) EXAMPLE 12Stabilisation of polymethylmethacrylate 100 Parts ofpolymethylmethacrylate (Resarit 400) are intensively mixed with 1.5parts of one of the additives listed in the following Table K. Theobtained mixture is extruded in a laboratory extruder, and subsequentlygranulated. The obtained granulate is afterwards regranulated a furthertimes. After the fifth, 15th and 25th extrusion, a specimen of thegranulate is pressed to form a 1 mm thick plate, which is assessed withrespect to its colour.

TABLE K Additive Colour of the synthetic material after:

No. 5 extrusions 15 extrusions 25 extrusions without addition yellowdeep yellow brown 1 colourles colourless faintly yellow 17 colourlesscolourless faintly yellow 18 colourless colourless faintly yellow 19colourless colourless faintly yellow We claim:

1. A composition of matter consisting essentially of an organic materialsubject to oxidative decomposition and from 0.01 to 5% by weight of theorganic material 55 of a stabilizer having the formula wherein A and Aare identicalor different and repre- 4. A composition of claim 3 whereinthe stabilizer is t the compound having the formula wherein R representsan alkyl group having 1 to 18 carbon atoms, or a phenyl group; and Xrepresents a bridging member -O- or -NH.

5. A ompositi'on of claim 3 wherein the stabilizer is the compoundhaving the formula 6. A composition of claim 3 wherein the stabilizer isthe compound having the formula 7. A composition of claim 13 wherein thestabilizer is the compound having the formula 2 24 C(CH3) C(CH HO O C Cn O OH g H N\ N C(CH C(CH 3 3 c ,OC H 3 3 OC H 8. Acomposition of claim3wherein the stabilizer is C(CH N C(CH 3 3 3 3 the compound having theformula l5 i OH 0 M c co 'OH C(CH N C(CH 1 l' N\ N Q HO o c c o"\. OH 2QC(CH c C(CH l 3 3 3 3 H I OC H N o.--:.--P C(Cl- C(C 12 s 17 o P 25 10.A composition of claim 1 wherein said organic material is selected fromthe group consisting of poly- 9. A composition of claim 3 wherein thestabilizer is amide, polyurethane, ethylene propyline-diene monothecompound having the formula mer rubber, polyacetal andpolymethylmethacrylate.

UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTIONPATENT NO. 3,900 ,443

DATED August 19, 1975 |NVENTOR(S) Christian Luethi, et a1 It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

Cover page, [73] Assignee, should read CIBA-GEIGY AG, Basle, SwitzerlandSigned and Scaled this Twenty-fifth Day Of October 1977 [SEAL] Attest:

RUTH C. MASON LUTRELLE F. PARKER Arresting Officer Acting Commissionerof Patents and Trademarks

1. A COMPOSITION OF MATTER CONSISTING ESSENTIALLY OF AN ORGANIC MATERIALSUBJECT TO OXIDATIVE DECOMPOSITION AND FROM 0.01 TO 5% BY WEIGHT OF THEORGANIC MATERIAL OF A STABILIZER HAVING THE FORMULA
 2. A composition ofclaim 1 wherein said organic material is poly- Alpha -olefin.
 3. Acomposition of claim 2 wherein said polyolefin is polypropylene.
 4. Acomposition of claim 3 wherein the stabilizer is the compound having theformula
 5. A omposition of claim 3 wherein the stabilizer is thecompound having the formula
 6. A composition of claim 3 wherein thestabilizer is the compound having the formula
 7. A composition of claim13 wherein the stabilizer is the compound having the formula
 8. Acomposition of claim 3 wherein the stabilizer is the compound having theformula
 9. A composition of claim 3 wherein the stabilizer is thecompound having the formula
 10. A composition of claim 1 wherein saidorganic material is selected from the group consisting of polyamide,polyurethane, ethylene propyline-diene monomer rubber, polyacetal andpolymethylmethacrylate.